JPH05134339A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To inhibit the occurrence of fog in a dot image and to ensure satisfactory dot performance as well as to ensure contrasty photographic characteristics even by processing with a developing soln. of <pH11 by incorporating a specified compd. CONSTITUTION:At least one kind of compd. represented by formula I is incorporated into a silver halide photographic sensitive material contg. a hydrazine compd. in at least one of the photographic constituent layers including a silver halide emulsion layer. In the formula I, each of R1 and R2 is alkyl, alkenyl, etc., L1 is a divalent combining group and R3 is a group represented by formula II, III or IV. In the formulae II-IV, G is carbonyl, sulfonyl, etc., X is H or a substitutable group, each of Y1-Y3 is alkyl, alkenyl, etc., each of Y4 and Y5 is alkyl, alkynyl, etc., when G is carbonyl, etc., Z is H or a substitutable group, and when G is sulfonyl, etc., Z is a substitutable group. The content of the compd. represented by the formula I is 5X10<-7>-5X10<-1>mol per 1mol silver halide.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material (hereinafter referred to simply as "light-sensitive material") capable of obtaining high contrast.
Also referred to as).

[0002]

BACKGROUND OF THE INVENTION The photomechanical process involves the conversion of continuous-tone originals into halftone images. In this step, a technique based on infectious development has been used as a photographic technique capable of reproducing an image in ultrahigh contrast.

The lith-type photosensitive material used for infectious development is
For example, the average grain size is 0.2 μm, the grain distribution is narrow, the grain shape is uniform, and the silver chloride content is high (at least 50
Mol% or more) consisting of silver chlorobromide emulsion. By treating this lith-type silver halide photographic light-sensitive material with an alkaline hydroquinone developer having a low sulfite ion concentration, an image having high contrast, high sharpness and high resolution can be obtained.

However, since these lith-type developers are susceptible to air oxidation, they have extremely poor preservability, and it is difficult to keep the development quality constant even during continuous use.

Without using the above lith developer,
A method for obtaining an image with high contrast is also known.
For example, U.S. Pat.No. 2,419,975, JP-A-51-16623 and 51-
As disclosed in Nos. 20921 and 56-106244, the photographic material contains a hydrazine derivative. According to these methods, the concentration of sulfite ion can be kept high in the developing solution, and the processing can be carried out in the state where the preservability is enhanced.

However, in these methods, in order to fully exhibit the high contrast of the hydrazine derivative, the pH value of 11 or more is used.
It had to be processed with a developer having a pH. pH11
The developer having a high pH as described above is more stable than the lith-type developer in which the developing agent is easily oxidized when exposed to air, but sometimes the ultrahigh contrast image cannot be obtained due to the oxidation of the developing agent.

In order to make up for this drawback, JP-A-63-29751 and European Patents 333,435 and 345,025 disclose a light-sensitive material containing a contrast-increasing agent which makes the contrast even in a developer having a relatively low pH. There is.

However, when a light-sensitive material containing such a contrast-enhancing agent is processed with a developing solution having a pH of less than 11, the contrast is insufficiently adjusted and satisfactory halftone dot performance cannot be obtained at present.

On the other hand, European Patent 364,166 and Japanese Patent Laid-Open Nos. 62-222241, 60-140340, 62-250439 and 62-
No. 280733, etc., describes a nucleation accelerator for accelerating the increase in contrast, and it is true that the addition of these compounds to the emulsion layer improves the halftone dot performance, but sand-like dots in the halftone dot, It has been found that a pin-shaped fog, that is, a black pin is generated, which causes a problem that the quality of a halftone image is impaired.

Therefore, a photosensitive material using an effective contrast enhancer and a nucleation accelerator that solves the above problems is desired.

[0011]

It is an object of the present invention to provide a halogenated compound which has a photographic characteristic of being hard even when processed with a developer having a pH of less than 11, and which has a good halftone performance by suppressing fog generated in a halftone image. It is to provide a silver photographic light-sensitive material.

[0012]

The above objects of the present invention have been achieved by the silver halide photographic light-sensitive material having the following constitution.

That is, a silver halide photographic light-sensitive material containing a hydrazine compound in at least one of photographic constituent layers including a silver halide emulsion layer contains at least one compound represented by the following general formula [I]. Silver halide photographic light-sensitive material.

[0014]

[Chemical 4]

In the formula, R ₁ and R ₂ each represent an alkyl group, an alkenyl group or an alkynyl group, L ₁ represents a divalent linking group, and R ₃ represents the following general formulas [II], [III] or (IV)
Represents a group represented by.

[0016]

[Chemical 5]

In the general formulas [II] to [IV], G represents a carbonyl group, a thiocarbonyl group, a sulfonyl group or an oxalyl group.

In the general formula [II], X represents a hydrogen atom or a substitutable group.

In the general formula [III], Y ₁ , Y ₂ and Y ₃ each represent an alkyl group, an alkenyl group or an alkynyl group.

In the general formula [IV], Y ₄ and Y ₅ each represent an alkyl group, an alkenyl group or an alkynyl group, and Z is G
Represents a hydrogen atom or a substitutable group when represents a carbonyl group or a thiocarbonyl group, and represents a substitutable group when G represents a sulfonyl group or an oxalyl group.

Next, the compound represented by the formula (I) of the present invention will be described in detail.

R ₁ and R ₂ are each an alkyl group (eg methyl, ethyl, propyl, i-propyl, butyl, octyl, dodecyl etc.), an alkenyl group (eg allyl, butenyl etc.), an alkynyl group (eg propargyl, butynyl). Etc.), and these are further suitable substituents (eg aryl group, alkoxy group, aryloxy group, hydroxyl group, alkylthio group, arylthio group, sulfonamide group, carbonamide group, ureido group, sulfamoyl group, carbamoyl group, Amino group, alkoxycarbonyl group, carboxyl group, etc.),
R ₁ and R ₂ may be linked to form a ring (for example, piperidine, piperazine, morpholine, pyrrolidine, etc.). R
Alkyl groups are preferred as ₁ and R ₂ and have _{2 to} 20 carbon atoms.
Most preferred are alkyl groups of

L ₁ represents a divalent linking group, preferably a group having an optionally substituted alkylene group (provided that the alkylene group is bonded to the (R ₁ ) (R ₂ ) N-group).

Among the divalent linking groups represented by L ₁ , more preferred are alkylene groups having 1 to 10 carbon atoms, and groups comprising a combination of alkylene groups having 1 to 10 carbon atoms and the groups shown below. Is mentioned.

[0025]

[Chemical 6]

R ₃ represents a group represented by the general formula [II], [III] or [IV].

In the general formula [II], examples of the substitutable group represented by X include an alkyl group (eg, methyl, ethyl, etc.), a carbamoyl group (eg, ethylcarbamoyl) and the like. The pyridine ring of the general formula [II] may further have a substituent (for example, an alkyl group) and may form a condensed ring (for example, quinoline).

In the general formula [III], Y ₁ , Y ₂ and Y ₃
Each represents an alkyl group (eg, methyl, ethyl, propyl, benzyl, etc.), an alkenyl group (eg, allyl, butenyl, etc.) or an alkynyl group (eg, propargyl, butynyl, etc.), and these are further suitable substituents (eg, aryl group). , Hydroxyl group, alkoxy group, aryloxy group, etc.). Y ₁ , Y ₂ and Y ₃
Is preferably a substituted or unsubstituted alkyl group.

Each of Y ₄ and Y _{5 in} the general formula [IV] represents an alkyl group, an alkenyl group or an alkynyl group. Preferred examples of each group are the same as Y ₁ to Y _{3 in} the general formula [III]. Groups may be mentioned.

Examples of the substitutable group represented by Z include the following groups.

When G is a carbonyl group, a thiocarbonyl group or a sulfonyl group, an alkyl group (eg methyl,
Ethyl, benzyl etc.), aryl group (eg phenyl), heterocyclic group (eg thienyl, furyl etc.), amino group (eg methylamino, dimethylamino, phenylamino etc.) or alkoxy group (eg methoxy, ethoxy etc.) Be done. When G is an oxalyl group, an amino group (eg, amino, methylamino, dimethylamino, phenylamino, benzylamino, etc.) or an alkoxy group (eg, methoxy, ethoxy, propyloxy, etc.)
Etc.

As G in the general formulas [II] to [IV], a carbonyl group is most preferable.

Representative specific examples of the compound represented by the general formula [I] are shown below.

[0034]

[Chemical 7]

[0035]

[Chemical 8]

[0036]

[Chemical 9]

[0037]

[Chemical 10]

Next, specific synthesis examples of the compound represented by the general formula [I] will be shown.

Synthesis Example 1 (Synthesis of Compound I-4) Compound I-4 can be synthesized according to the following synthetic method.

[0040]

[Chemical 11]

Synthesis Example 2 (Synthesis of Compound I-8) Compound I-8 can be synthesized according to the following synthetic method.

[0042]

[Chemical 12]

Synthesis Example 3 (Synthesis of Compound I-15) Compound I-15 can be synthesized according to the following synthetic method.

[0044]

[Chemical 13]

The content of the compound represented by the general formula [I] of the present invention is 5 × 10 ^{−7 to} 5 × 10 5 per mol of silver halide.
^-1 mol is preferable, and particularly 5 × 10 ^{-6 to} 5 × 10 ^-2
A molar range is preferred.

In the present invention, when the compound represented by the general formula [I] is contained in the light-sensitive material, it is contained in the silver halide emulsion layer or the hydrophilic colloid layer adjacent to the silver halide emulsion layer. The compound of the general formula [I] may be contained in the same layer as the hydrazine compound or may be contained in a different layer.

As the hydrazine compound used in the present invention, those represented by the following general formula [H] are preferable.

[0048]

[Chemical 14]

In the formula, A represents an aliphatic group, an aromatic group or a heterocyclic group, B represents an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, an alkoxy group, an aryloxycarbonyl group, Sulfamoyl group, sulfinamoyl group,
It represents an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group, an oxalyl group or a heterocyclic group, and A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group, a sulfonyl group or an oxalyl group.

However, B, A ₂ and the nitrogen atom to which they are bound may form a partial structure —N═C═ of hydrazone.

The details of the compound represented by the general formula [H] are described in Japanese Patent Application No. 3-286619.

Among the hydrazine compounds used in the present invention, particularly preferred are the compounds represented by the above general formula [V].

[0053]

[Chemical 15]

The general formula [V] will be described in more detail.

The aryl group represented by R ₄ is preferably monocyclic or bicyclic, and examples thereof include a benzene ring and a naphthalene ring.

The heterocyclic group represented by R ₄ is preferably a monocyclic or bicyclic 5- or 6-membered unsaturated heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen. , Quinoline, pyrimidine, thiophene, furan, thiazole, benzothiazole ring and the like. An aryl group is preferred as R ₄ , and a benzene ring is most preferred.

A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl, trifluoroacetyl, benzoyl etc.), a sulfonyl group (methanesulfonyl, toluenesulfonyl etc.) or an oxalyl group (eg etoxalyl). ), But both are preferably hydrogen atoms.

R ₅ represents a —N (R ₆ ) (R ₇ ) group or a —OR ₈ group,
Here, R ₆ and R ₇ are each a hydrogen atom, an alkyl group (methyl, ethyl, benzyl, etc.), an alkenyl group (allyl, butenyl, etc.), an alkynyl group (propargyl, butynyl, etc.), an aryl group (phenyl, naphthyl, etc.). , Heterocyclic groups (2,2,6,6-tetramethylpiperidinyl, N-benzylpiperidinyl, quinuclidinyl, N, N'-diethylpyrazolidinyl, N-benzylpyrrolidinyl, pyridyl, etc.), Amino group (amino, methylamino, dimethylamino, dibenzylamino, etc.), hydroxyl group, alkoxy group (methoxy, ethoxy, etc.), alkenyloxy group (allyloxy, etc.), alkynyloxy group (propargyloxy, etc.), aryloxy group ( phenoxy), a heterocyclic oxy group (pyridyloxy, etc.), ring together with the nitrogen atom in R ₆ and R ₇ (piperidine, Moruho It may be formed down, etc.). R ₈ is a hydrogen atom, an alkyl group (methyl, ethyl,
Methoxyethyl group, hydroxyethyl, etc.), alkenyl group (allyl, butenyl, etc.), alkynyl group (propargyl, butynyl, etc.), aryl group (phenyl, naphthyl, etc.), heterocyclic group (2,2,6,6-tetramethyl) Piperidinyl, N-methylpiperidinyl, pyridyl and the like).

Specific examples of the compound represented by the general formula [V] are shown below. However, the present invention is not limited to these.

[0060]

[Chemical 16]

[0061]

[Chemical 17]

[0062]

[Chemical 18]

[0063]

[Chemical 19]

[0064]

[Chemical 20]

The method for synthesizing the hydrazine compound used in the present invention is described in JP-A-62-180361, JP-A-62-178246, and JP-A-63-234.
No. 245, No. 63-234246, No. 64-90439, JP-A-2-37,
2-841, 2-947, 2-120736, 2-230233,
3-125134, U.S. Pat.Nos. 4,686,167, 4,988,604,
4,994,365, European Patents 253,665, 333,435.
You can refer to the method described in the issue.

The content of the compound represented by the general formula [V] of the present invention is 5 × 10 ^{−7 to} 5 × 10 5 per mol of silver halide.
^-1 mol is preferable, and particularly 5 × 10 ^{-6 to} 5 × 10 ^-2
A molar range is preferred.

In the present invention, the compound represented by the general formula [V] is contained in the light-sensitive material in a silver halide emulsion layer or a hydrophilic colloid layer adjacent to the silver halide emulsion layer.

The silver halide emulsion can be coated directly on the support or can be coated through another layer, for example, a hydrophilic colloid layer containing no silver halide emulsion, and further halogenated. A hydrophilic colloid layer as a protective layer may be coated on the silver emulsion layer. Further, the silver halide emulsion layers may be separately coated on each of the silver halide emulsion layers having different sensitivities, for example, high sensitivity and low sensitivity. in this case,
An intermediate layer may be provided between each silver halide emulsion layer.
That is, an intermediate layer made of a hydrophilic colloid may be provided if necessary. Further, between the silver halide emulsion layer and the protective layer,
A non-photosensitive hydrophilic colloid layer such as an intermediate layer, a protective layer, an antihalation layer and a backing layer may be provided.

Next, the silver halide used in the light-sensitive material of the present invention will be described. 4 mol% as silver halide
The following silver iodide, preferably silver chloroiodobromide or silver iodobromide containing 3 mol% or less of silver iodide. The average grain size of the silver halide grains is preferably in the range of 0.05 to 0.5 μm, and particularly preferably 0.10 to 0.40 μm.

The grain size distribution of the silver halide grains used in the present invention is arbitrary, but the monodispersity value defined below is from 1 to 20.
% Is preferable, and more preferably 5 to 15%.

Here, the monodispersity is defined as a value (%) obtained by multiplying a value (variation coefficient) obtained by dividing the standard deviation of particle diameter by the average particle diameter by 100. For the sake of convenience, the grain size of silver halide grains is represented by the edge length in the case of cubic grains, and the other grains (octahedral, tetradecahedral, etc.) are calculated by the square root of the projected area.

When the present invention is carried out, for example, as a grain of silver halide, a grain type having a multi-layered laminated structure of at least two layers can be used. For example, silver iodobromide in the core portion and shell portion can be used. A silver iodobromide grain having silver bromide can be used. At this time, iodine can be contained in any layer within 5 mol%.

The silver halide grains used in the silver halide emulsion of the present invention include a cadmium salt, a zinc salt, a lead salt, a thallium salt and an iridium salt (including a complex salt) in the process of forming and / or growing the grain. ), A rhodium salt (including a complex salt) and an iron salt (including a complex salt), at least one metal ion is added to allow the metal element to be contained inside the particle and / or on the surface of the particle. It is also possible to impart a reduction sensitizing nucleus to the inside of the grain and / or the grain surface by placing it in a suitable reducing atmosphere.

Furthermore, the silver halide can be sensitized with various chemical sensitizers. Examples of the sensitizer include active gelatin, sulfur sensitizer (sodium thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, etc.), selenium sensitizer (N, N-dimethylselenourea, selenourea, etc.) ), Reduction sensitizers (triethylenetetramine, silver tin 1 tin, etc.), such as potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, 2-aurosulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chloro. Various noble metal sensitizers represented by platinate and sodium chloroparadite can be used alone or in combination of two or more. When a gold sensitizer is used, rodan ammon can be used as an auxiliary agent.

The silver halide grains used in the present invention can be preferably applied to grains having a surface sensitivity higher than the internal sensitivity, that is, silver halide grains giving a so-called negative image. Performance can be improved.

The silver halide emulsion used in the present invention is a mercapto heterocyclic compound (1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole),
Benzotriazoles (5-prombenzotriazole-5
-Methylbenzotriazole), benzimidazoles (6-nitrobezoimidazole) and the like can be used for stabilization or fogging suppression.

The photosensitive silver halide emulsion layer or its adjacent layer is provided with a Research Disclosure for the purpose of increasing sensitivity, increasing contrast or promoting development.
ure) 17463 Nos. ΧΧΙ items B to D can be added.

The polyethylene oxide derivatives described in Japanese Patent Application No. 2-160539, pages 94 to 96 (exemplified compounds P-1 to P-
17) is preferably added.

The polyethylene oxide derivative has a molecular weight of 1500
The above is preferable. The addition amount is preferably in the range of 0.01 to 4.0 mol, and more preferably 0.02 to 2.0 mol, per mol of silver halide. Further, it is desirable to contain it in the emulsion layer.

A sensitizing dye, a plasticizer, an antistatic agent, a surfactant, a hardener and the like may be added to the silver halide emulsion used in the present invention.

When the compounds of the general formulas [I] and [V] according to the present invention are added to the hydrophilic colloid layer, gelatin is suitable as the binder for the hydrophilic colloid layer, but hydrophilic colloids other than gelatin are preferred. Can also be used. These hydrophilic binders are 10 g / each on both sides of the support.
It is preferable that the coating is performed at m ² or less.

Examples of the support usable in the practice of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, and polyester film such as polyethylene terephthalate. These supports are appropriately selected depending on the intended use of the silver halide photographic light-sensitive material.

To develop the light-sensitive material of the present invention, the following developing agents are used, for example.

Typical examples of HO (CH = CH) nOH type developing agents include hydroquinone, and catechol, pyrogallol and the like.

Further, as the HO (CH = CH) nNH ₂ type developer, ortho and para aminophenols or aminopyrazolones are typical ones, and N-methyl-p-aminophenol, N-
Examples include β-hydroxyethyl-p-aminophenol, p-hydroxyphenylaminoacetic acid, and 2-aminonaphthol.

Heterocyclic type developers include 1-phenyl-3
-Pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl
Examples thereof include 3-pyrazolidones such as 3-pyrazolidone.

Others, TH. James: The Theory of the Photographic Process 4th Edition
Theory of the Photographic Process, Fourth Editio
n) pages 291-334 and Journal of the American
Chemical Society (Journal of the American Chem
ed., Vol. 73, p. 3100 (1951), which can be effectively used in the present invention. These developers may be used alone or in combination of two or more kinds, but it is preferable to use two or more kinds in combination.

The effect of the present invention is not impaired even if a sulfite such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the light-sensitive material of the present invention. Further, hydroxylamine or a hydrazide compound may be used as a preservative. In addition, it is possible to provide a pH adjusting function and a buffering function with caustic alkali, alkali carbonate or amine as used in general black and white developers.

The developer used in the present invention is characterized in that a developer having a pH of less than 11 can be used. In addition, the developer includes an inorganic development inhibitor such as promkari and an organic development inhibitor such as 5-methylbenzotriazole, 5-methylbenzimidazole, 5-nitroindazole, adenine, guanine, 1-phenyl-5-mercaptotetrazole, and ethylenediamine-4. Metal ion capture agents such as acetic acid, methanol, ethanol,
Benzyl alcohol, development accelerators such as polyalkylene oxides, sodium alkylaryl sulfonates, natural saponins, surfactants such as sugars or alkyl esters of the above compounds, hardening agents such as glutaraldehyde, formalin, glyoxal, sodium sulfate It is optional to add an ionic strength adjusting agent or the like.

The developer used in the present invention contains alkanolamines such as diethanolamine and triethanolamine, and diethylene glycol as an organic solvent.
Glycols such as triethylene glycol and alkylamino alcohols such as diethylamino-1,2-propanediol and butylaminopropanol may be contained.

[0091]

EXAMPLES Specific examples of the present invention will be described below, but embodiments of the present invention are not limited to these.

Example 1 (Preparation of silver halide emulsion A) A silver iodobromide emulsion (2 mol% of silver iodide per 1 mol of silver) was prepared by the simultaneous mixing method. During this mixing, K ₂ IrCl ₆ was added at 8 × 10 ^-7 mol per mol of silver. The obtained emulsion was an emulsion composed of cubic monodisperse grains (coefficient of variation 9.5%) having an average grain size of 0.20 μm.
After adding 6.5 ml of 1% potassium iodide aqueous solution per mol of silver to this emulsion, modified gelatin (exemplified compound G-8 of Japanese Patent Application No. 1-180787) was added to carry out Japanese Patent Application No. 1-180787. It was washed with water and desalted in the same manner as in Example 1. PA at 40 ° C after desalting
g was 8.0. Further, at the time of redispersion, a mixture of the following compounds [A], [B] and [C] was added as an antibacterial agent.

[0093]

[Chemical 21]

(Preparation of silver halide photographic light-sensitive material) One of 100 μm-thick polyethylene terephthalate films having a 0.1 μm-thick undercoat layer on both sides (see Example 1 of JP-A-59-19941) On the undercoat layer, a silver halide emulsion layer of the following formulation (1) was applied so that the amount of gelatin was 2.0 g / m ² and the amount of silver was 3.2 g / m ² , and then the following formulation The emulsion protective layer of (2) is coated so that the amount of gelatin is 1.0 g / m ² , and
On the other undercoat layer on the other side, apply a backing layer of the following formulation (3) so that the amount of gelatin will be 2.4 g / m ² ,
Further, a backing protective layer having the following formulation (4) was coated thereon so that the amount of gelatin would be 1.0 g / m ² , and samples 1 to 26 were obtained.

Formulation (1) (Silver halide emulsion layer composition) Gelatin 2.0 g / m ² Silver halide emulsion A (silver amount) 3.2 g / m ² Sensitizing dye (SD-1) 8 mg / m ² Sensitizing dye (SD-2) 0.2 mg / m ² stabilizer (ST-1) 30 mg / m ² antifoggant (adenine) 10 mg / m ² surfactant (saponin) 0.1 g / m ² surfactant (SU-1) 8.0 mg / m ² Hydrazine derivative of the present invention (shown in Table 1) 30 mg / m ² Nucleation promoting compound of the present invention (shown in Table 1) 100 mg / m ² Latex polymer (LP-1) 1 g / m ² Polyethylene glycol (MW = 4000) 0.1g / m ² Hardener (H-1) 60mg / m ² Formulation (2) (Emulsion protective layer composition) Gelatin 1.0g / m ² Surfactant (SU-2) 10mg / m ² Matting agent (silica with an average particle size of 3.5 μm) 3 mg / m ² Hardener (formalin) 30 mg / m ² Surfactant (SU-3) 10 mg / m ² Prescription (3) (Backing layer composition) Irradiation prevention Dye (AI-1) 30mg / m ² Irradiation prevention dye (AI-2) 75mg / m
² Irradiation prevention dye (AI-3) 30mg / m ² Gelatin 2.4g / m ² Surfactant (SU-1) 6.0mg / m ² Surfactant (saponin) 0.1g / m ² Formulation (4) ( Backing protective layer composition Gelatin 1g / m ² Matting agent (polymethylmethacrylate with an average particle size of 3.0 to 5.0μm) 15mg / m ² Surfactant (SU-2) 10mg / m ² Hardener (glyoxal) 25mg / m ² Hardener (H-1) 35 mg / m ² Additives used in each formulation are as follows.

ST-1: 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene H-1: 2,4-dichloro-6-hydroxy-s-triazine / sodium SU-2: sulfosuccinic acid di (2-ethylhexyl) ester / sodium SU-3: sulfosuccinic acid di (2,2,3,3,4,4,5,5,6,6,7,7-
Dodecyl fluoroheptyl) ester sodium

[0097]

[Chemical formula 22]

[0098]

[Chemical formula 23]

The obtained sample was subjected to a halftone dot quality test by the following method.

(Test method for halftone dot quality) A stepped wedge was partially attached with a return halftone screen (150 lines / inch) having a halftone dot area of 50%, and the sample was brought into close contact with it and exposed for 5 seconds with a xenon light source. This sample was developed with an automatic processor for rapid processing in which the following developer and fixer were added under the following conditions, and the halftone quality of the sample was observed with a magnifying glass of 100 times. The item is ranked as "5", and the following "4", "3",
The rank was sequentially lowered to "2" and "1" and evaluated in five levels. Incidentally, the ranks "1" and "2" are levels that are not practically preferable.

The fog in the halftone dots is also evaluated in the same manner, and the one having no black pin in the halftone dot is set to the highest rank "5", and the black pin occurrence in the halftone dot is determined. The evaluation was performed by sequentially lowering the rank to “4”, “3”, “2”, and “1”. Incidentally, in the ranks "1" and "2", the black pin is large, which is a level that is not preferable in practical use.

Developer Formulation (Developer 1) Developer 1 Ethylenediaminetetraacetic acid sodium salt 1g Sodium sulfite 60g Trisodium phosphate (12-hydrate) 75g Hydroquinone 22.5g Sodium hydroxide 8g Sodium bromide 3g 5-Methylbenzotriazole 0.25g 1-phenyl-5-mercaptotetrazole 0.08g metol 0.25g water to make pH = 10.8 to adjust the developer at 1000ml sodium hydroxide 2: Fixing what is a same composition as the developer solution 1 was adjusted to pH = 10.5 Liquid formulation (composition A) Ammonium thiosulfate (72.5w / v% aqueous solution) 240ml Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid 6g Sodium citrate dihydrate 2g (Composition B) Pure water (ion exchange water) 17ml Sulfuric acid (50% w / w aqueous solution) 4.7 g Aluminum sulphate (Al ₂ O ₃ converted content is 8.1 w / w% aqueous solution) 26.5 g When using the fixing solution, dissolve the above composition A and composition B in 500 ml of water in this order. , It was used after finishing to 1 liter. The pH of this fixer was adjusted to 4.8 with acetic acid.

(Development processing conditions) (Process) (Temperature) (Time) Current image 40 ℃ 15 seconds Settlement 35 ℃ 15 seconds Water wash 30 ℃ 10 seconds Dry 50 ℃ 10 seconds Prescription (1) The following compounds (a) and (b) were added as comparative compounds to the nucleation-accelerating compound of the present invention added to the silver halide emulsion layer.

[0104]

[Chemical formula 24]

The results are shown in Table 1.

[0106]

[Table 1]

As is clear from Table 1, the samples according to the present invention have good halftone dot quality and black pins for comparison.

[0108]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material having high contrast and little fog even when it is processed with a developing solution having a low pH of less than pH 11.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material containing a hydrazine compound in at least one of photographic constituent layers including a silver halide emulsion layer, containing at least one compound represented by the following general formula [I]. A silver halide photographic light-sensitive material characterized by the above. [Chemical 1] In the formula, R ₁ and R ₂ each represent an alkyl group, an alkenyl group or an alkynyl group, L ₁ represents a divalent linking group, and R ₃
Represents a group represented by the following general formula [II], [III] or [IV]. [Chemical 2] In formulas [II] to [IV], G represents a carbonyl group, a thiocarbonyl group, a sulfonyl group, or an oxalyl group. In formula [II], X represents a hydrogen atom or a substitutable group.
In the general formula [III], Y ₁ , Y ₂ and Y ₃ each represent an alkyl group, an alkenyl group or an alkynyl group. General formula (I
V], Y ₄ and Y ₅ each represent an alkyl group, an alkenyl group or an alkynyl group, Z represents a hydrogen atom or a substitutable group when G is a carbonyl group or a thiocarbonyl group, and G is a sulfonyl group. In the case of a group or an oxalyl group, it represents a substitutable group. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the hydrazine compound is a compound represented by the following general formula [V]. [Chemical 3] In the formula, R ₄ represents an aryl group or a heterocyclic group, and R ₅ is-.
Represents an N (R ₆ ) (R ₇ ) group or a —OR ₈ group (R ₆ and R ₇ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, a hydroxyl group. , An alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group or a heterocyclic oxy group, R
₈ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group). A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group,
Represents a sulfonyl group or an oxalyl group.